Method of making rubber-fiber articles



July 11, 1933. a. DEWEY 11,917,755

METHOD OF MAKING RUBBER FIBER ARTICLES Filed Aug. e, 1952 March 5,

Patented...July- 11, 1,933

UNITED STATES 1,917,155 PATENT@ OFFICE BRADLEY DEWEY, 0F CAMBRIDGE, MASSACHUSETTS, ASSIGNOR T0 DEWEY AND ALMY CHEMICAL COMPANY, OF'CAMBRIDGE'MASSACHUSETTS, .A CORPORATION OIF M+SSA.-

CHUSETTS METHOD or maxime RUBBER-FIBER ARTICLES yApplication led August 1932Serial No. 627,737., and'in Great Britain May`30, 1931.

This invention relates to the production of miscellaneous articles composed of fibers associated intimately with rubber coherently coagulated in situ from an aqueous. dispersion thereof and isa continuation in part of myapplication Serial Number 344,145, filed 1929. Objects of the invention are to render the mutual association of rubber and 'iiber more rapid, more uniform, and morecertainly controllable than has been the case heretofore. For example, United States Patent No. 1,- 671,914, dated May 29, 1928, to lrVilliam Burton VVescott', describes a fiber-reinforced rubber articles which, While practically operative and commercially used, involves several disadvantageous features W-hichit is my object to eliminate. 'lhe employment of an active coagulant to coagulate latex rubber in a fibrous structure saturated with latex initially. sets a close-textured though reticulate skin of coagulated rubber at the surfaces of the structure, strains, retards, and even prevents a comlete and uniform' dissemination of the coagulant throughout the latex-impregnated librous mass; and theslow diffusion of the coagulant through the outer skin which initially forms results in a further thickening and condensation of coagulated rubber locally and towardthe surface, i. e., the particles of the latex diffuse outwardly from the interior to meet the slowly incoming wave of 'coagulant panying coagulation at the .interior. V But even a greater disadvantage arises from the fibrous structure therewith, be the impregnapartial, and by thesubsetion complete or of these physical conditi ons quent alteration f ronrthosewhich preclude Acoagula'nt activi` ty'io `the dormant" coagula'nt Vto those which process .of making l which reand are coagulated in .situ thereby, which practically prevents thorough penetration of the coagulant to and accomrender the coagulant active. More specilically, my invention is characterized by the preparation of a composition of latex and a substance dispel-sible therein which comprises or contains a coagulant inactive, or dormant, at relatively low temperature, e. g. room temperature, but which becomes active at a higher temperature, e. g. 150 F. to 212 F., giving aproduct characterized by an open texture'and permeable structure, as Well as remarkable uniformity and homogeneity.

The literature relating to latex and its treatment furnlshes quite numerous examples of latex coagulantswhich are inert or dormant in the presence of coagulation buf-` fers, with which, therefore, mixtures with latex can be made which remain stable Without coagulation; others which though dispersed in latexremain inactive so long as the alkalinity of the emulsion is4 unaltered but operate as coagulants whenas by evaporation of ammonia from the emulsion-the alkali-nity falls below a critical value; and others which are dormant at relatively low'temperatures but become fully active when a higher temperature is reached. In some cases the coagulative ingredient is ever present, but its inliuence is suppressed and subdued by the -imposed physical conditions; while.l in other cases no coagulative agent exists untilthere occurs an alteration in the imposed physical conditions which incites a chemical change productive within the mass of a new material coagulative of latex.

For the purposes of this specification and the, claims attached to. it, I use lthe term dormant coagulant as'definitive of any substance o`r compound (physical or chemical) which,miscible and dispersible in latex emul. sion'is inactive therein under imposed physical conditions, but becomes active to coagulate the latex rubber when the coagulationprecluding condition is supplanted by another physical condition undcr which the coagulant, previously dormant, becomes active. By the, term inactive therein I intend to embrace, as more fully hereinafter described, those. materials which at ordinary'workroomv temperature do not convert the latex to a. mass iowing less readily, or act aswh'at is knownin the art as thickening agents, but are, as the words imply. without appreciable tect upon the latex. I have discovered that` all vdormant-coagulant, latex compounds in wh ich the stite of subdivision 'oftheeolloid alf;-

rio i rubber particles remains substantially the same as it was in the untreated latex, i. e., substantially unaggregated or unthickened as exemplified in my preferred example given below, are e'ective for use in all applications of my invention.

In the present specification and claims it is necessary sharply to differentiate between dormant coagulant'latex Compounds which aggregate to form only cheesy or caseous coagula when the necessary physical stimuli are supplied, and those which' coagulate to a coherent continuum. -Materials of the former class are not operative for the purposes of the present invention and the phrase becomes active to coagulate the latex rubber denotes only those materials which under the conditions of -use result in a 'coherent unified rubber mass when the/stimuli which incite the dormant coagulant to activity are applied. This distinction is necessary because many of the dormant coagulants as described and as used in the prior art are productive of the caseoustype of eoagula, but` not the coherent reticulate type of coagulum here required, and furthermore because the term coagulation is often used to embrace anyirreversible coalescence of the latexparticles, be it to discrete aggregates or to the true coherent retieulate coagulum. Thus, for example, the latter materials may be sometimes advantageously used and have been employed in the preparation of dipped articles and coated fabrics where the syneresis or shrinkage of a coherent reticulate coagulum is often objectionable and where such shrinkage may be avoided by the production of the Caseous type of coagulation, of which the resulting discrete particles become unified only on drying. The suitability in this respect of a dormant coagulant latex compound to the purposes of the pl'esent invention may be determined by subjecting a small quantity of the material to be tested per se -to-the' physical influences which induce activation thereofl and observing the resulting type of coagulation. If the particles merely aggregate to form a ilocculent, cheesy, or caseous non-coherent fluid mass, the material is not suited; but if a coherent, unified rubber coagulum is formed, the dormant coagulant latex com'- pound may be employedfor the purposes of the resent invention.

. iscroscopic observation of the inception of caseous coagulation discloses the formation of aggregates nf'varying sizes cha raeterized by dense packing of the laten particles within the aggregate; while a coherent eoagulum results from the arrangement of the latex particles in thread-like processes which unite to form 'an open-textured reticulate continuum. In thevcase of caseous coagula,

' the latex particles coalesee to form discrete or aggregates which remain more or le dispersedly suspended in the continuous watery phase; whereas in the ease ot coherent coagulmthe particles form a continuous coherent network permeated by the watery phase. It is the formation of this coherent structure to which the present invention is vlimited and to which I restrict the meaning at ordinary or easily imposed temperatures,

but which ateasily obtainable higher temperatures becomes active. Salts which pro- -vide bior tri-valent metal ions may constitute such dormant coagulants of which the behavior is determinable by temperature, being substantially inert while a mixture oflatex and the sol or solution ot' salts is relatively cool, and becoming active when the temperature is raised to or above a critical value. For example, 0.15% (on a 30% latex) of a water-soluble calcium salt may form with normal alkaline laitex a relatively stable mixture at ordinary room temperatures, but coagulates the latex at about 200O F. W'hile dormant coagulant latex compounds of the bi' or tri-valent 1n xtal salt type may be employed, however, their use is not generally recommended because it is ditlicult to control and maintain their characteristics within the necessary narrow limits. Unless certain precautions are taken, bi-- or tri-valent metal ions tend to thicken latex compounds by inducing incipient aggrega- Vtion of the latex particles, thereby reducing their capability of penetrating small intel'- liber spaces and thus untitting the material for the purposes of this invention. All commercial latex contains some small aggregates; but so long as the size of the aggregates in the latex compound, be they normally present or induced therein, is suiliciently small to permit their penetrating the interstices of' the librous structure employed, their presence is not obJectionablc. The -criterion of adaptability 1n tlnsrespeetis whether or not lthe dormant coagulant latex compound is capable of penetrating and satin-ating the interstices of the fibrous structure. `vhich is to be treated. lf the latter is relativelyclosetextured, sucl1 as a dense felt. for example, a compound possessing the iuidity and penetrating characteristics of latex freed from lits normally present cream may be required i.-e., one which is substantially free from aggregated latex particles. If on the other hand, the fibrous material to be saturated is relatively open-textured, such as a loose longliher hat, the presence of minute aggregates may not be seriously object ionable.` Aggregation of latex particles to the point of sensible thnflmning, whether it be a cream of As stated, bior tri-valent metal ions tend 'to cause incipient aggregation and an excess of these ions may completely aggregate the latex particles into-caseous coagula. There are further disadvantages in the use of the salts of the bior tri-valent metals in that v there-are several variables to contend with in preparing therefrom dormant coagulant latex compounds suitablefor the impregnation of fibrous structures. Thus the tendency to thicken latex, or aggregate the particles thereof, exhibited by the ions of these metals is accentuated by long standing, increases gradually with increase of temperature and dependsv in part on the stability of the latex. By selecting a latex of relatively high stability and ascertaining by experiment the minimum amount of metal ions requisite toproduce a coherent coagulum at the activating temperature in that vparticular latex, the permissible storage time and temperature maybe found vby trial. Protective colloids capable of completely suppressing the tendency of bior tri-valent metal ions to thicken latex or incipiently aggregate its particles at normal temperature prevent, in general, the formation of a coherent coagulum at the activating temperature, and usually cause the ultimate coagulation to be of the caseous type. Certain heat-coagulable proteins, however, may be used which, while effectively preventing any substantial thickening of the latex compound under the influence of the bior tri-valent metal ions at normal temperatures, will themselves coagulate at or below the activating temperature of the dormant coagulant and thereupon cease tion as protectives. Upon the heat nullication of the protective effect of these coagulable proteins, the metal ions assert their full coagulative influence upon the unprotected latex particles and a coherent coagulum results. Among the heat-nullifiable protectives suitable for the purpose of this invention the following are mentioned' in the order of their preference hemoglobin, egg albumin, and serum albumin.

A composite of latex and dormant coagulant whichI have found to be especially effective in carrying out my process and which I submit as a preferred example, is formed by adding to 300 parts of a normal alkaline latex (which contains about 30% of rubber and .8% of ammonia) 42 parts of a solution prepared by dissolving 10 parts of granulated zinc chloride in 160 parts of Water and to funcslowly adding thereto with stirring 15 parts of 28 B. commercial ammonia water.

This mixture of latex and dormant coz'igulant is remarkably stable at ordinary temperatures and lup to about F., the emulsion of rubber particles remaining unaifected, so that the composite will permeate and saturate permeable bodies as readily as latex alone. At or above 150o F., however, the previously dormant coagulantbecomes active, and its coagulant etl'ect is, at such temperatures, so rapid as to be practically instantaneous. The zinc of the preferred dormant coagnlant latex compounds described abovey is present as a complex zinc ion tZn(NH) .-L") which is not coagulative of latex but which under the influence of heat undergoesI dissociation with the liberation of free zinc cations which are strongly coagulative of latex. Cadmium salts also form vith ammonia similar heat-dissociable complex ionsand may be substituted for zinc chloride in the above cited example. Latex compounds prepared with their aid. however. are not so stable as those obtained by using zinc chloride or othersoluble Zinc salts which obviously may 'be employed with equally good results.

Any permeable tibrus structure (fleece, felt` bat, etc.) such as above described, contains in its interber spaces, wherein the composite has penetrated, both the latex rubber ofl the emulsion and the coagulant which is ready to act whenever and wherever the physical condition (e. g. temperature) preclusive of coagulant activity is superseded by a physical condition, different inkind or degree (e. g. higher temperature) which renders the thcrctofore dormant coagulant active.

For further illustration of .my process,

reference may be had to the drawing which. illustrates schematically 1n cross section porsuitably formed conductor such as C which should so nearly tit the dimensions of the fibrous sheet as to l'prevent escape of the latex composite therefrom. During the impregnation and conveyance of the impregnated sheet to thel device for producing initial coagulation, the conditions (as of temperature) which maintain its dormant state are maintained. It may be advisable `initially to supersede the physical saturated with a composite the coagulant in conditions which preclude activity of the dormant coagulant .b'y conditions which operate to make this coagulant active at lor near the surface of the fibrous body F. Forcinstance, steam jet pipes S may be provided to spurt jets of hot steam on the two sides of the fibrous sheet. This'steam raising the temperatures of the surfaces of the sheet to 150 F. or over activates the theretofore dormant coagulant and effects. a coagulation of the latex rubber at and near the surfaces so that a thin film of coherently coagulated rubber .extends over bot-l1 surfaces and serves to retard and practically prevent any escape of the latex composite containeduin the lbody of the fibrous sheet and also any penetration of water intothe sheet during the next stage of operation, but does not, because of its extreme thinness, seriously impede the subsequent drying operation. The sheet then proceeds into'a heating tank T through a suitable aperture at I where it comes4 in contatc with body of `water W which is heated to a temperature, high enough to activate the coagulantvassociated with the latex. The Water also floats the impregnatedy fibrous sheet and thus relieves it of any stresses which might tend to distort or injure it. Preferably, also, the upper part offthe covered tank Tis filled withv hot'steam which issues from perforations in a steam-spraying pipeS1, so thatcoagulant-activating temperature conditions are maintained above as Well as below the impregnated sheet.- The length' of the tank T and the rate of progress of the fibrous sheet F are determined to the end that when the fibrous sheet'is led from the tank through a. suitable aperture as at O, the coagulantfactivating temperature will have been imposed upon the latex composite land all parts thereo For still further illustration of .a manner in which the fibrous material may be impregnated and the rubber coagulated, reference may be had to a detailed procedure which may bc used for the manufacture of shoe soles. I proceed by saturating a thick, open-textured felt or bat in a bath of dormant coagulant latex compound prepared according to my preferred example given above. The wet material is subjected to light pressure, such as by pressing between open set squeeze rolls to remove the excess saturant. The impregnated material is then placed in a chamber filled with a mixture of steam and hot air so that a dry bulb temperature of about 150 C. anda wetbulb temperature of about -90o C.

obtains. Ihe temperature of the impregnated mass is rapidly raised and the rubber of the saturant coagulated to form a coherent reticulate structure. The relatively high humidity afforded by the steam greatly facilitates the conduction of heat into the material `and'minimizes an objectionable surface evaporation.

The composite impregnant of the fibrous structure carrying as it does both the latex Arubber and the coagulant therefor, and this coagulant being almost instantaneously active as soon as the critical temperature is reached, the coagulation of the latex rubber willl be uniform and rapid. In this respect it may be stated that the process of the present invention Ydiffers in physical principle from the before-mentioned Wescott process in that coherent coagulation throughout the mass results from conductance of heat instead of fluid coagulant thereinto; and this difference not only permits of much more rapid vcoagulation in the present instance, but also, as already stated, results in uniform rubber distribution free from the thick impervious outer skin which has tremendously impeded subsequent drying in otherwise similar processes practised in the prior art.

After the fibrous structure with its uniformly distributed content of coagulated rubber has emerged from the coagulating tank or heating chamber, the liquid remaining in the interstices or voids of the structure may be expressed, and the rubberized fibrous structure washed by alternate applications of clear water and expression thereof, and finally dried. Although the latter operation is preferably carried out in` vacuum, it is quite practical to dry the product of this in- ,vention in an ordinary dryin oven at atmos- I pheric pressure This is in s arp contradis tinction to the veryeXpensive and cumbersome processes required by similar articles pre# pared in the prior art; and the extreme ease with which the excess moisture of the product of this invention may be removed by desiccation is most surprising and unexpected and constitutes one of the principal advantages thereof. After drying, the material maybe compressed so as to eliminate the voids of the L reticulum and to integrate all of the rubber into a substantially continuous and impermeable body reinforced by the including fibers. These subsequent manipulations are not illustrated by the drawing since they are the same in general character as those which have previously been applied -to `latex-impregnated fiber structures.

The addition and distribution in the latex composite of a vulcanizing agent will not at all interfere with the process above described and will, of course, prepare the latex rubber for vulcani'zation. v

In these specifications and the claims which follow, except where otherwise particularly designated, I usethe word latex as definitive and inclusive of water dispersions of rubber generally, whether artificially pre- Vpared as by emulsification of rubber previously coagulated or cured, or the normal latex which contains about 30% solids in the water dispersion of Revertex, in which the concentration of rubber is frequently as high as 70%. The technique to be followed in carrying out the method herein described will vary with the latex employed. For instance, a Revertex, diluted if need be to facilitate irn- E pregnation of a fibrous structure, usually need not be alkaline to the degree `necessary with normal latex in order to form stable compositions with dormant coagulants. The protective colloids incorporated in Revertex constitute buffers against coagulation, even if the Revertex be faintly'alkaline or even neutral. In many eases these are beneficial in that they impart greater stability to the compound in the dormant state, but necessitate,

nevertheless a higher concentration of potential coagulant than is demanded by ordinary latex; but in other cases and with certain dormant coagulants the supplementary protective constituents of the Revertex are detrimental since they cause coagulation of the objectionable caseous type.

l claim:

1. Method of depositing latex rubber in l i a close-textured permeable fibrous structure ated bythe watery phase, and (4) removing water therefrom.

2. Method of depositing latex rubber in a close-textured permeable fibrous structure vcomprising (l) dispersing a dormant coagulant in latex under` conditions to prevent thickening, (2) filling -interfiber spaces of a close-textured permeabley fibrous structure with the composite of latex and dormant coagulant, 3) activating the dormant coagulant in the lat'eX throughout the body of. said saturatedfibrous structure to coagulate said latex to form throughout said structure a continuous coherent rubber network permeated by the watery phase, and (4) removing waterl therefrom by drying.

3. Method of depositing lateX rubber in a close-textured permeable fibrous structure comprising (l) dispersing a dormant coagulant in latex under conditions to prevent thickening, v(2) filling interfiber spaces ofia close-textured permeable fibrous structure with' the composite of latex and dormant coagulant, (3) activating the dormant coagulant in the latex throughout the body of said y saturated fibrous structure to coagulate said latex to form throughout said structure a.

continuous coherent rubber network pernicated by the ,watery phase, and (4) removing water therefrom by expression and drying.

c: 4. Method of depositing latex rubber in a structure with close-textured permeable fibrous structure' comprising (l) dispersing a heat-activable dormant coagulant 1n latex under conditlons 4to prevent thickening, (2) filling interfiber spaces of a vclose-textured permeablev fibrous structure with the composite of latex and dormant coagulant, (3) raising the temperature throughout the body of said saturated fibrous structure to activate the dormant coagulant in the latex to coagulate said latex to form throughout said structure a continuous coherent rubber network permeated by the watery phase, and(4) removing Awater therefrom.

5. Method of depositing latex rubber in a close-textured permeable fibrous structure comprising (l) dispersing a heat-activable dormant coagulant in latex under conditions to prevent thickening, (2) filling-interfiber spaces of a close textured permeable fibrous the composite of latex and dormant coagulant, (3) raising the temperature throughout the body of said saturated fibrous structure to activate the dormant coagulant in the latex to coagglate said latex to form throughout said structure a continuous coherent rubber network permeated by the watery phase, and (4) removing water therefrom by drying.

6. Methodof depositing latex rubber in a close-textured permeable fibrous structure comprising (l) dispersing a heat-activable dormant coagulant in latex under conditions to prevent thickening, (2) filling `interfiber spaces of a close-textured permeable fibrous structure with the composite of latex and ,f

dormant coagulant, raising the temperature throughout the body of said saturated fibrous structure to activate the dormant c0- -agulant in the latex to coagulate said latex -to form throughout said structure a continuous' coherent rubber network permeated by the watery phase, and (4) removing water therefrom by expression and drying.

7 Method of depositing latex rubber in a permeable fibrous structure comprising (l) dispersing'ammoniated zinc chloride in latex, (2) filling interfiber `spaces of a permeable fibrousstructure with the composite of latex and ammoniated zinc chloride, (3) raising the temperature throughout the body of said saturated fibrous structure to activate the ammoniated zinc chloride in the latex to coagulate said latex to form throughout said structure a continuous coherent rubber network permeated by the watery phase, and (4) removing waterv therefrom.

8. Method of depositing latex rubber in a permeable fibrous structure comprising (l) -dispersing ammoniated zinc chloride in latex,

(2) filling interfiber spaces of a permeable fibrous structure with the composite of latex ammoniated zinc chloride in the latex to coagulate said latex to form throughout said structure a continuous coherent rubber net-- ammoniated zinc chloride in the latex to coagulate said latex to form throughout said structure a continuous coherent rubber network permeated by the watery phase, and (4) removing water therefrom by expression and drying.4

10. Method of depositing latex rubber in a close-textured permeable fibrous structure comprising (1) dispersing a bi-valent or tri-valent `metal salt in latex in such quantity and under such conditions as to prevent thickening at lower temperatures but to cause coherent coagulation of the latex when the temperature is raised, (2)v filling interfiber spaces of a close-textured permeable fibrous structure with the composite of latex and bi-valent or tri-'valent metal salt, (3) raising the temperature throughout the body of said saturated fibrous structure to activate the vbi-valent or tri-valent metal salt in the latex to coagulate said latex to form throughout said structure a continuous coherent rubber network permeated by .the watery phase, and (4) removing water therefrom.

11. .Method of depositing latex rubber ina close-textured permeable fibrous structure comprising (1) dispersing a bi-valent or trivalent metal salt in latex in such quantityand under such conditions as to. prevent thickening at lower temperatures but to cause coherent coagulation of the latex when the temperature is'raised,` (2) filling inter.

fiber spaces of a close-textured permeable fibrous structure with the composite oflatex protective, (2)l filling interber spaces of a and bi-valent or tri-valent metal salt, (3) raising the temperature throughout the body of said saturated fibrous structure to activate the bi-valent or tri-valent metal salt in the latex to coagulate said latex toform throughout said structure a continuous coherent rubber vnetwork permeated by the watery phase, and (4) removing water therefrom by drying. i

12. Method of depositing latex rubber in a close-textured permeable fibrous structure comprising (l) dispersilig a bi-valent or trivalent metal salt in latex in such quantity and under such conditions as to prevent thickening at lower temperatures but to cause coherent coagulation of the latex when the temperature is raised, (2) filling interl fiber spaces of a close-textured permeable fibrous structure with the composite of 1atex and bi-valent or tri-valent -metal salt, (3) raising the temperature throughout the body of said saturated fibrous structure to activate thefbi-valent or tri-valent metal salt in the latex to coagulate said latex to form throughout said structure a continuous coherent rubberpnetwork permeated by the watery phase, and (4) removing water therefrom by expression and drying.

13. Method of depositing latex rubber in a permeable fibrous structure comprising 1) dispel-sing a bi-valent or tri-valent metal salt in latex containing a heat-coagulable protective, g2) filling interfber spaces of a permeable brousstructure with-the composite of latex, bi-valent or tri-valent metal salt, and heat-coagulable protective, (3) raising the temperature through the body of said saturated fibrous structure to coagulate the protective and activate the bi-valent or tri-valent metal salt in the latex to coagulate said'latex to form throughout said structure a continuous coherent rubber network permeated. by the watery phase, and (f4) removing water' therefrom.

-14. Method ofldepositing latex rilbbe;` in a permeable fibrous structure comprising (l) dispersing abi-valent or tri-valent metal salt in latexcontaining a heat-coagulable protective, (2) filling interfiber spaces of a permeable fibrous structure with the composite lot latex, bi-valent or tri-valent metal salt, and heat-coagulable protective, (3) raising the temperature vthroughout the body of said saturated fibrousstructure to coagulate the protective and activate the bi-valent or tri-valent metal salt in the latex to coagulate said latex to form throughout said structure a continuous coherent rubber network permeated by the watery phase, and (4) removing water therefrom by dr ing.

15. Method of depositing latex ru 1) dispersing a bi-valent-or tri-valent metal salt i-n latex containing -a heat-coagulable permeable fibrous structure with the composite of latex, bi-valent or tri-valent metal 'v salt, and heat-coagulable protective, (3)

.. raising the temperature throughout thebody ber in.

* a permeable fibrous structure comprising agulate said latex to form throughout said structure a continuouscoherent rubber network permeated bythe watery phase, and (4) removing water therefrom by expression i BRADLEY DEWEY.

me `at/Cambridge, Massa- 

